Vat color composition for printing



Patented July 25, 1944 VAT COLOR COMPOSITION OR PRINTING Roy Herman Kienle and Chester Albert Amlck,

Bound Brook, N. J., assignors to American Cyanamld Company, New York, N. Y., a corporation of Maine No Drawing. Application February 24, 1942, Serial No. 432,158

v 14 Claims. This invention relates to an improved vat dye composition and particularly to improved vatdye printing pastes. 7

In the past there has been a demand for improved brightness of shade and levelness of dyeing in dyeing procedures employing vat dyes. The problem is particularly serious in vat dye printing and many compounds have been, used to improve shade and other dyeing or printing characteristics. Frequently in the past some compounds have been used which produce one type of result in dyeing and another in printing, but the problem still remains a serious one.

The present invention deals with vat dye compositions containing a small amount of an ester of a polycarboxylic acid having at least one sulfonic group, the alcohol radicals of the esters being aliphatic alcohols of more than 3 and less than carbon atoms. Improved results are obtained with the vat dye compositions of the present invention regardless of whether they are used for dyeing or printing. In other words, the present invention produces improvements in both procedures by the addition of the same class of material. However, the improvements are much more striking. when the vat dye compositions of the present invention are used in printing, that is to say when they have associated with them the customary printing thickening ingredients such as gums, reducing agents, alkalis and the like.

Various sulfopolycarboxylic acids may be used in making the ester, for example, those described in the patent to J ae ger, U. S. 2,028,091 issued J anuary 14, 1936, among which the sulfosuccinates are preferred as they are'readily available commercially in large quantities and give excellent results.

The present invention is not limited to any particular vat dye or to any particular proportion of ester to dye except that the amount of ester should be small. It is an advantage that the presentinvention gives improved results when used in conjunction with the ordinary types of printing thickener and requires no new technique in the compounding or use of the printing paste.

The reason for the improved brightness and fullness of shade is not fully known and the present invention is not intended to be limited to any exact theory of operation. It is very probable, however, that the action is not solely that of a powerful dispersing or wetting agent, for although the esters of the sulfopolycarboxylic acids are well-known as powerful wetting agents, they are in no sense the equivalent of other wetting agents or deflocculating agents in their action on printing pastes. In fact. it is desirable, although not essential, that other dispersing or deflocculating agents be used in obtaining a high degree of dispersion of the vat color before incorporating the printing thickening. The action of the sulfodicarboxylic esters is quite different from that of other wettingagents, althoughas has beenstated above, the precise reasons for the difference of behavior are not fully known.

In addition to the fuller shade the present invention when applied to printing with vat dyes has further important advantages. When a rough'fabric such as wool is printed, it is important that the surface fibers or fuzz be colored. Otherwise the uncolored surface fuzz dulls the shade and obscures the true color. invention produces a remarkable improvement in this respect, the improvement being so great that it is even noticeable with fabrics having a relatively smoother surface, such as satins. The reason for the improved results on surfaces which present the above problem is also not fully known and it is not intended to limit the invention to any theory of action. It is possible that the improved results are caused by the same factors which improve the brightness and fullness of shade, but it may be that a plurality of factors and that diilerent factors play a part in producing theimproved result. Another, and most surprising property of printing compositions utilizing the present invention is the fact that these compositions may be used in printing on fabrics which are very sensitive to alkali, such as for example, wool. In fact. it had been considered impracticable to print most vat dyes onto wool by any ordinary printing means because of damage to the wool from the alkali necessarily present in the printing paste. Compositions of the present invention, however, may be used with care in printing wool in the case of many vat dyes, and this is of tremendous practical value because of the enormous fastness of many vat dyes which did not find counterparts in most of the types of dyes suitable for printing wool. The reason why wool can be printed with some vat dye compositlOIlS utilizing the present inven on is also not fully known and it is not desired or intended to innit-this feature of the invention to any theory of action. It seems probable, however, that some other factors may be playing a part in wool printmg results although it is possible that the same factor which gives brighter shades also permits wool printing. The result, however, is most surprising, because there are The present a number of agents Whlch have been added to vat dye compositions to improve color but so far as applicants are aware 1100) are deflocculated with one part of the sonone or these added agents have made p ss ble act as such rather than in the form of reaction products.

The length of carbon chains in the alcohol used to make the ester is critical, but it is not necessary to use alcohols of either straight or branched chain, both types work satisfactoril but somewhat better results are obtained with branched chain alcohols, particularly with lower molecular weight alcohols.

The invention will be described in greater detail in conjunction with the specific examples, which represent typical printing pastes. The composition of the printing thickener itself not being novel, the following two typical printing thickeners will be described in conjunction with examples.

Psnsrmc Tmcxzmm A 2,000 parts of 177 British gum (Stein-Hall) are slurried with 5,000 parts of water and then heated in a double boiler with continuous stirring until the slurry has reached a temperature of 185' F. Heating is continued for 90-120 minutes. 450 parts of powdered potassium carbonate and 450 parts of .powdered sodium carbonate are then added and stirred until dissolved. The source of heat is removed and stirring continued until the mix is approximately 150 F. at which time 700 parts of sodium sulfoxylate formaldehyde are added and stirred until solution is complete. After 600 parts of glycerine have been added, the contents are bulked to 10,000 parts with water and stirring continued until the paste has cooled to approximately room temperature.

Pam'rrmi Tmcxsmza B A printing thickener is prepared by heating 720 parts of 3-2 British gum and 720 parts of dextrine-converted starch of low solubility in 5,600 parts of water in a double boiler with continuous stirring at a temperature of 185-190 F., for approximately 90 minutes. The source of heat is removed, the stirring continued and the gum is cooled to a temperature of approximately 120 F. 1,200 parts of potassium carbonate are dissolved in 1,000 parts of water (heating if necessary) and added to the cooked gum. 1,560 parts of sodium sulfoxylate formaldehyde are dissolved in 1,500 parts of water, heating to a temperature of 140 F. After the potassium carbonate solution has been thoroughly stirred into the gum mix, the sodium sulfoxylate formaldehyde solution is added and stirring continued until the whole is thoroughly mixed. Finally, 360 parts of glycerine are added and after thorough stirring, the whole is bulked to 12,000 parts.

Example 1 100 parts of Navy Blue 'NT wet press cake condium salt of disulfo dinaphthyl methane and adjusted with water to contain 14.2 parts of real' color. Five parts of this slurry are mixed with 5 parts of water and 00 parts of thickener B.

Thislsusedasacontrol sample.

Asecondfivepartsotthisslurryismixed m.

5 parts of a, 8% water solution of the sodium di-isobutylsulfosuccinate and 90 parts of thickener B. The pastes are printed on pigmented rayon and cotton, air dried, aged in a steam ager, oxidized in an oxidizing solution, soaped in a 0.1% soap solution at the boil for 5 minutes, rinsed, squeezed and ironed dry. The prints obtained from the-paste that contained the sodium isobutylsulfosuccinate are very much stronger than the prints obtained from the water dispersion of the press cake on both cotton and the pigmented rayon.

Example 2 The procedure of Example 1 was followed except that instead of sodium di-isobutylsulfosuccinate sodium dioctylsulfosuccinate was used. The prints obtained from the paste that contained the sodium dioctylsulfosuccinate are very much stronger than the prints obtained from the water dispersion of the press cake on both cotton and the pigmented rayon.

Example 3 The procedure of Example 1 was followed except that instead of sodium di-isobutylsulfosuccinate sodium dihexylsulfosuccinate was used. The prints obtained from the paste that contained the sodium dihexylsulfosuccinate are very much stronger than the prints obtained from the water dispersion of the press cake on both cotton and the pigmented rayon.

Example 4 The procedure of Example 1 was followed except that instead of sodium di-isobutylsulfosuccinate sodium di -amylsulfosuccinate was used. The prints obtained from the paste that contained the sodium di-amylsuliosuccinate are very much stronger than the prints obtained from the water dispersion of'the press cake on both cotton and the pi mented rayon.

Example 5 The pastes are printed on pigmented rayon cotton as in Example 1.

The prints obtained from the pastes that contain the sodium isobutylsulfosuccinate are very much stronger-than the prints from the water dispersion of the press cake on both cotton and pigmented rayon.

Example 6 The procedure of Example 5 was followed except that instead of sodium di-isobutylsulfosuccinate sodium dioctylsulfosuccinate was used.

The prints obtained from the pastes that contain the sodium dioctylsulfosuccinate are very taining about 18.3 parts of real dye (color index much stronger than the prints from the water pigmented rayon.

water and 90 parts of thickener B. This is used dispersion of thepress cake onboth cotton and Example 7 Example 8 The procedure of Example was 'followed except that instead of sodium di-isobutylsulfosuccinate sodium di-amylsulfosuccinate was used.

The prints obtained Pom the pastes that contain the sodium di-amylsulfosuccinate are very much stronger than the prints from the water dispersion of the press cake on both cotton and pigmented rayon.

Example 9 Ten parts of the Hydron Orange R slurry prepared in Example 2 were mixed with 5 parts of 3-A alcohol and 85 parts of thickener B. This is used as a control sample. 1

A second ten parts of the slurry is mixed with five parts of a 6% alcohol solution of the sodium di-isobutylsulfosuccinate and 85 parts of thickener B. These pastes are printed, on pigmented rayon and cotton as in Example 1. The prints obtained from the paste that contained the sodium isobutylsulfosuccinate are very much stronger than the prints made from the water-v alcohol dispersionof the press cake on both cotton and pigmented rayon.

Example 10 The procedure of Example 9 was followed except that instead of sodium di-isobutylsulfosuccinate sodium dioctylsulfosuccinate was used. The prints obtained from the paste that contained the sodium dioctylsulfosuccinate are very much stronger than the prints made from the water-alcohol dispersion of the press cake on both cotton and pigmented rayon.

Example 11 Example 12 The procedureof Example 9 was followed except that instead of sodium di-isobutylsulfosuccinate sodium di-amylsulfosuccinate was used. The prints obtained from the paste that contained the sodium di-amylsulfosuccinate are very much stronger than the prints made from wateralcohol dispersion of the press cake on both cotton and pigmented rayon.

Example 13 A sample of Yellow GC wet press cake (color index 1095) is dispersed with the sodium salt of disulfo dinaphthyl methane and adjusted with water to contain about 10% real color. Five parts of this slurry is mixed with five parts of as a control sample.

A second five parts of the slurry is mixedwith five parts of a 6% water solution of the sodium di-isobutylsulfosuccinate and 90 parts of thickener- B. These pastes are printed on pigmented rayon and cotton-as in Example 1.

The prints obtained from the paste that contained the sodium isobutylsulfosuccinate are very much stronger than the prints from the water dispersion of'the press cake on both cotton and the pigmented rayon.

Example 14 The procedure of Example 13 wasffollowed except that instead of sodium di-isobutylsulfosuccinate sodium di-amylsulfosuccinate was used.

The prints obtained from the paste that contained the sodium di-amylsulfosuccinate are very much stronger than the prints from the water dispersion of the press cake on both cotton and the pigmented rayon.

Example 15v Asample of Golden Orange G (color index 1096) is dispersed with 'a sodium salt of disulfo dinaphthyl methane and adjusted with water to contain about 9.75 parts'of real dye. Five parts of this slurry-is mixed with five additional parts of water and 90 parts of Printing thickener B.

A A second five parts of the slurry is mixed with flve parts of a 6% solution of the sodium di-isobutylsulfosuccinate and 90 parts of thickener B. The pastes are printed on pigmented rayon and cotton as in Example 1.

The prints obtained ;from the paste that contain the sodium isobutylsulfosuccinate are very much stronger than the prints from the water dispersion from the press cake on both cotton and pigmented rayon.

Example 16 The procedure of Example 15 was followed except that instead of sodium di-isobutylsulfosuccinate sodium dioctylsulfosuccinate was used.

The prints obtained from the paste that contains the sodium dioctylsulfosuccinate are ve y much stronger than the prints from the water dispersion from the press cake on and pigmented rayon.

Example 17 The procedure of Example 15 was followed except that instead of sodium di-isobutylsiulfosuccinate sodium dihexylsulfosuccinate was used.

The prints obtained from the paste that contains the sodium di-hexylsulfosuccinate are very both cotton much stronger than the prints from the water dispersion from the press cake on both cotton and pigmented rayon.

Example 18 The procedure of Example 15 was followed except that instead of sodium di-isobutylsulfosuccinate sodium di-amylsulfosuccinate was used.

The prints obtained from the paste that contains the sodium di-amylsulfosuccinate are very much stronger than the prints from the water on both cotton and pigmented rayon.

Example 19 5 parts of a dispersible Violet RRN (color inparts of thickener A. This is used as a control sample.

A second 5 parts of the same color is pasted with 5 parts of water and'8 parts oi the sodium di-amylsulfosuccinate and 87 parts of thickener A.

These printing color pastes are then printed on textile fabrics dried in a hot air dryer at a low temperature, aged in a steam ager, treated with an oxidizing solution, rinsed, soaped in a 0.1% soap solution for 5 minutes at the boil, again rinsed, and dried.

The prints made from the paste containin the sodium di-amylsulfosuccinate gave noticeably stronger color yield on pigmented rayon than the prints made from the paste which contained only water.

Example 20 The procedure of Example 19 was followed except that instead of sodium di-amylsulfosuccinate sodium dihexylsulfosuccinate was used. The prints made from the paste containing the sodium dihexylsulfosuccinate gave noticeably stronger color yield on pigmented rayon than the prints made from the paste which contained only water.

Example 21 The procedure of Example 19 was followed generally except that a dispersible, Hydron Orange R Powder (color index 1217) containing approximately 1.2 parts real dye is pasted with 3 parts of water and 2 parts of the sodium dioctylsuli'osuccinate. This is then pasted with 90 parts of thickener A and tested on pigmented rayon and 80 x 80 bleached unmercerized cotton rint cloth.

Prints obtained from the paste containing the sodium dioctylsulfosuccinate were stronger on pigmented rayon than the prints from the paste which contained water only.

Example 22 The procedure of Example 19 was followed except that 5 parts of a dispersible Vat Scarlet 2GHN Powder, which is a mixture of Hydron Orange (color index 1217) and Hydron Pink FF (6-6 dichloro 4,-4' dirnethyl 2-2' bis-thionaphthene indigo), powder prepared according to U. S. P. Reissue 21,402 and containing approximately 1.8 parts real color, is used in place of the Violet RRN, with 2 parts of the sodium di-amylsulfosuccinate and 3 parts of water.

The prints obtained from the paste which contained the sodium di-amylsulfosuccinate are much stronger than the prints made from the paste which contained water only.

The printing color pastes after standing approximately 24 hours, are again printed on pigmented rayon and on cotton. Again the prints made from the paste that contained the sodium di-amylsulfosuccinate are much stronger than the prints made from the paste which contained water only.

' Example 23 5 parts of the dispersible Hydron Scarlet 2GHN Powder are pasted with 2.5 parts of water, 1.5 parts of the butyl ether of ethylene glycol and 1 part of the sodium di-amylsulfosuccinate. 90 parts of thickener A are then added and thoroughly mixed. This is printed on 80 x 80 bleached, unmercerized cotton print cloth, and titanium dioxide pigmented viscose rayon fiat crepe, together with a control sample prepared by pasting 5 parts of the Scarlet ZGHN Powder with 5 parts of 'water and then mixing with parts of thickener A. After ageing, oxidizing, soaping, and drying, the prints obtained item the paste containing the sodium di-amyl uifosuccinate and the butyl ether or ethylene 818001 are much stronger than the prints made from the paste which contains water only.

Example 24 The procedure of Example 23 is followed except that instead or sodium di-amylsulfosuccinate sodium dihexylsulfosuccinate is used. After ageing, oxidizing, soaping, and drying, the prints obtained from the paste containing the sodium dihexylsulfosuccinate and the butyl ether of ethylene glycol are much stronger than the prints made from the paste which con water only.

Example 25 grams of the dispersible Vat Scarlet 2GHN double type are milled for 15 hours with 10 parts of the sodium diamylsulfosuccinate. In another experiment 50 parts of the same color are milled with 10 parts of the sodium diamylsulfosuccinate and 40 parts of cerelose.

Both of these products ground rather easily as the organic ester was quite friable. Both samples were then print-tested against the original dispersed Vat Scarlet 2GHN Double Powder at equivalent strengths using thickener A.

The print stripes obtained from the pastes which contained the dry-blended sodium diamylsulfosuccinate were much stronger than the stripes which were obtained from the paste which contained no dry blending material.

Example 26 isobutylsulfosuccinate are print-tested against,

an equivalent amount of the same color which has not been dry-blended. Prints from the paste containing the sodium di-isobutylsulfosuccinate are stronger than the prints obtained from the sample which contained no printing assistants, on pigmented and spun rayon.

Example 27 10 parts of a Jade Green (color index 1101) color paste and containing about 1.26 parts real color are mixed intimately with 90 parts of thickener B. This printing color paste is divided into two halves. one of which is used as a control. To the second half is added one part of sodium di-isobutylsulfosuccinate and then thoroughly incorporated into the printing color paste. This product and the control are printed on a piece of woolen flannel, aged in a steam ager for 10 minutes, then oxidized, soaped, rinsed and dried. The prints obtained from the paste that contained the sodium di-isobutylsulfosuccinate are much stronger than the prints obtained from the blank. Furthermore, the loose woolen fibers on the surface are colored giving a smooth, even print when the sodium di-isobutylsulfosuccinate is used, and when this assistant is not used the surface is covered with undyed fibers. Also the the blank.

Example 28 Example 2'7 is repeated using an acetate faced satin with rayon back instead of the woolen flannel.

Again the prints from the paste containing the sodium di-isobutylsulfosuccinate are stronger, much more level and solid than the prints from th blank.

Example 29 alyst, and then sulfonating the ester by heating to 80 C. for about 24 hours 100 parts oi the ester with a solution of 35 parts of sodium bisulfite in 35 parts of water and '70 parts of methanol.

Prints made with the above composition show brighter and fuller shades than corresponding prints without the butyl suli'ocarbailylate.

We claim:

l. A vat, dye composition comprising a disperse vat dyestufl. and an efiective amount of an ester of a sulfopolycarboxylic acid with aliphatic alco hols having more than 3 and less than 10 carbon atoms at least 10% by weight of the real dyestufl.

2. A vat dye composition comprising a dispersed vat dyestui! and an effective amount of an ester of an aliphatic sulfopolycarboxylic acid with aliphatic alcohols having more than 3 and less than 10 carbon atoms at least 10% by weight of the real dyestufl'.

3. A vat dye composition comprising a dispersed vat dyestufi and an effective amount of an ester of a sulfosuccinic acid with aliphatic alcohols having more than 3 and less than 10' carbon atoms at least 10% by weight of the real dyestumi 4. A vat dye composition comprising a dispersed vat dyestuil. and an effective amount of a dioctylsulfosuccinate at least 10% by ,weight of the real dyestufl.

5. A vat dye composition comprising a dispersed vat dyestufl. and an effective amount of a diamylsuli'osuccinate at least 10% by weight ofthe real dyestufl. v

6. A vat dye printing composition comprising a dispersed vat dyestufl, printing thickener, re-

(ill

ducing agent and an efiective amount of an ester of sulfopolycarboxylic acid with an aliphatic alcohol having more than 3 and less than 10 carbon atoms at least 10% by weight of the real dyestuff.

'7. A vat dye printing composition comprising a dispersed vat dyestufi, printing thickener, reducing agent and an eflectiv'e amount of an ester of an aliphatic sulfopolycarboxylic acid with an aliphatic alcohol having more than 3 and less than 10 carbon atoms at least 10% by weight of the real dyestufi.

8. A vat dye printing composition comprising a dispersed vat dyestuff, printing thickener, reducing agent and an effective amount of an ester of sulfosuccinic acid with an aliphatic alcohol having more than 3 and less than 10 carbon atoms at least 10% by weight of the real dyestufi.

9. A vat dye printing composition comprising a dispersed vat dyestufi, printing thickener, reducing agent and an effective amount of a dioctylsulfosuccinate at least 10% by weight of the real dyestuii'.

10. A vat dye printing composition comprising a dispersed vat dyestuif, printing thickener, reducing agent and an effective amount of a diamylsulfosuccinate at least 10% by weight of the real dyestuff.

11. A method of printing fabrics containing basic nitrogeneous fibers which comprises printing a pattern on the fabric by means of a printing composition comprising a dispersed vatdyestuif, printing thickener, reducing agent, alkali, and an effective amount of an ester of a sulfopolycarboxylic acid with aliphatic alcohols having more than 3 and less than 10 carbon atoms at least. 10% by weight of the real dyestufi.

12. A method of printing. fabrics containing basic nitrogeneous fibers which comprises printing a pattern on the fabric by means of a printing composition comprising a dispersed vat dyestufi, printing thickener, reducing agent, alkali, and an effective amount of an ester of a sulfosuccinic acid with aliphatic alcohols having more than 3 and less than 10 carbon atoms at least 10% by weight of the real dyestuif.

13. A method of printing fabrics containing basic nitrogeneous fibers which comprises printing a pattern on the fabric by means of a printing composition comprising a dispersed vat dyestuil, printing thickener, reducing agent, alkali, and an effective amount of a dioctylsultosuccinate at least 10% by weight of the real dyestufl.

14. A method of printing fabrics containing basic nitrogeneous fibers which comprises printing a pattern on the fabric by means 01' a printing composition comprising a dispersed vat dyestufl', printing thickener, reducing agent, alkali, and an eflective amount of a diamylsulfosuccinate at least 10% by weight of the real dyestuti.

ROY HERMAN KIENLE. crmsm ALBERT AMICK. 

